Photoinduced [6 ]-Electrocyclic Reaction of Mono-, Di-, and Trisubstituted Triphenylamines in Acetonitrile. A Steady-State Investigation

AL POSTIGO *; BEATRIZ LANTAÑO; IVAN ROMERO; BONESI, SERGIO M.

JOURNAL OF ORGANIC CHEMISTRY

AMER CHEMICAL SOC

Lugar: Washington; Año: 2022 vol. 87 p. 13439 - 13454

0022-3263

Direct irradiation of mono-, di-, and trisubstituted triphenylamine derivatives in acetonitrile as solvent with light of 254 nm has been systematically investigated, revealing that the exo/endo carbazole derivatives were formed as the main photoproducts from modest to good yields for triphenylamines substituted with electron-donor and neutral substituents. The kinetic profiles of the photoreaction were also recorded, and the consumption rate constants (k) were measured. These kinetic parameters show dependence on the nature of the substituents, and linear Hammett correlations were carried out to showcase the substituent effect. On the other hand, the spectroscopic behavior of the electron-rich substituted triphenylamines has been analyzed, suggesting that the fluorescence emission spectra display a mirror image of the lower energy absorption bands, while for those amines bearing electron-acceptor groups the formation of charge-transfer complexes and their fluorescence emissions constitute the main deactivation pathway of the photoreaction.